EP0469659A1 - Simultaneous elimination of SO2 and H2S from off gases - Google Patents

Simultaneous elimination of SO2 and H2S from off gases Download PDF

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EP0469659A1
EP0469659A1 EP91201757A EP91201757A EP0469659A1 EP 0469659 A1 EP0469659 A1 EP 0469659A1 EP 91201757 A EP91201757 A EP 91201757A EP 91201757 A EP91201757 A EP 91201757A EP 0469659 A1 EP0469659 A1 EP 0469659A1
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stage
suspension
zno
zns
sump
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German (de)
French (fr)
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EP0469659B1 (en
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Hans-Joachim Dr. Röhrborn
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GEA Group AG
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Metallgesellschaft AG
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
    • B01D53/52—Hydrogen sulfide
    • B01D53/523—Mixtures of hydrogen sulfide and sulfur oxides

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  • the invention relates to a method for the simultaneous removal of S0 2 and H 2 S from exhaust gases.
  • the invention is therefore based on the object to provide a method for the simultaneous removal of S0 2 and H 2 S from exhaust gases which can be carried out inexpensively and with which the limit values of TA ships from 27.2.1986 for S0 2 and H 2 S in clean gas fall relatively short.
  • the object on which the invention is based is achieved in that the exhaust gas containing S0 2 and H 2 S in a first stage with a first suspension containing 60 to 95 g / l ZnS0 3 and 80 to 90 g / l ZnO and 0.1 to 1.0 g / l of ZnS is brought into contact in countercurrent, 40 to 60% by volume of the suspension obtained in the bottom of the first stage containing 20 to 35 g / l of ZnS and 130 to 145 g / l of ZnS0 4 and Contains 0.1 to 8 g / l of ZnS0 3 , withdrawn from the bottom of the first stage and again continuously fed into the first stage at the top of the first stage, so that the exhaust gas depleted in the first stage of S0 2 and H 2 S Head of the first stage is withdrawn and in a second stage with a second suspension containing 80 to 150 g / l ZnO and with a third suspension containing 60 to 95 g / l Zn
  • the suspensions circulated in the first and second stages are aqueous suspensions whose pH values are 2.0 to 5.5. It has surprisingly been found that with the method according to the invention, the pollutants H 2 S and S0 2 are almost completely removed from exhaust gases, even if they are present in the exhaust gas in a fluctuating concentration ratio.
  • the method according to the invention enables a largely quantitative reaction of the reactants in the first and second stages due to the relatively high mean sprinkling density of 20 to 60 m 3 / (m 2 .h), so that the removal of the pollutants H 2 S and S0 2 from exhaust gases is carried out inexpensively.
  • a preferred embodiment of the invention consists in using ordered washing columns as the first stage and / or as the second stage.
  • ordered washing columns is to be understood as meaning those packed columns in which the packed bodies are arranged according to a certain system in accordance with their geometric shape. Packings consisting of prefabricated, ordered elements can also be used. If ordered wash columns are used as the first stage and / or the second stage, the pressure loss in the individual stages is advantageously reduced.
  • the second stage is arranged on the first stage within a separation column.
  • part of the suspension obtained in the bottom of the first stage is removed from the first stage and 48 to 97% H 2 S0 4 is added to a pH of 0.6 to 1.0.
  • H 2 S0 4 is added to a pH of 0.6 to 1.0.
  • part of the suspension obtained in the bottom of the first stage is removed from the first stage and Cl 2 is added to a pH of 1.3 to 1.8.
  • Cl 2 is added to a pH of 1.3 to 1.8.
  • the sulfur resulting from the chlorination is then filtered off from the solution.
  • the figure shows the schematic structure of a column with the first and second stage.
  • the figure shows a column (11) in which the first stage (1) and the second stage (2) are arranged one above the other.
  • the exhaust gas (4) containing S0 2 and H 2 S is passed horizontally into the first stage (1) and brought into contact with a suspension (5a) containing ZnS0 3 , ZnO and ZnS in countercurrent.
  • the following chemical reactions take place, with the required oxygen being removed from the exhaust gas:
  • a suspension (8) is obtained which contains ZnS, ZnS0 4 and ZnS0 3 .
  • This suspension (8) is removed from the bottom (1b) of the first stage (1) from the column (11).
  • a portion (8b) of this suspension (8) is fed to the head (1a) of the first stage (1) via a pump (13) and again brought into contact with the exhaust gas (4) containing SO 2 and H 2 S in countercurrent.
  • the other part (8a) of the suspension (8) is removed from the system via the three-way valve (12) and worked up either by adding H 2 S0 4 or Cl 2 .
  • the depleted of S0 2 and H 2 S exhaust gas (9) is removed at the top (1a) of the first stage (1) and fed to the second stage (2) above the sump (2b).
  • the exhaust gas (9) depleted of SO 2 and H 2 S is mixed with a second suspension (6) containing ZnO and with a third suspension (5b) containing ZnO, ZnS0 3 and ZnS, brought into contact in countercurrent.
  • Part of the suspension (5) obtained in the sump (2 b) of the second stage (2) is used as the third suspension (5 b).
  • the suspensions (6) and (5b) are mixed with one another via a mixing point (7).
  • the pollutants H 2 S and S0 2 react with the ZnO according to the following reaction equations:
  • the other part (5a) of the suspension (5) is discharged via the three-way valve (3) and fed into the first stage (1) at the head (1a).
  • the clean gas (10) is discharged from the second stage at the head (2a).
  • 700 m 3 / h of an exhaust gas (4) which contains 980 mg / Nm 3 dry SO 2 and 300 mg / Nm 3 dry H 2 S, are a first stage (1), which is designed as an ordered wash column, supplied and brought into contact in countercurrent with 5 m 3 / h of a first suspension (5a) containing 62.7 g / l ZnS0 3 , 85.5 g / l ZnO and 0.3 g / l ZnS.
  • the average pH is 2.0.
  • the sprinkling density in the first stage (1) is 40 m 3 / (m 2 .h).
  • This second stage (2) is also designed as an ordered wash column.
  • the exhaust gas (9) depleted in SO 2 and H 2 S is in the second stage with 5 m 3 / h of a suspension (6) which contains 117 g / l of ZnO and with 4.8 m 3 / h of a third suspension ( 5 b), which contains 62.7 g / I ZnS0 3 , 85.5 g / I ZnO and 0.3 g / I ZnS and that of the suspension (5) obtained in the sump (2 b) of the second stage (2) is removed, brought into contact in countercurrent.
  • the average pH of the second stage is between 5.0 and 5.5.
  • the sprinkling density in the second stage (2) is 40 m 3 / (m 2 .h).

Abstract

A process is described for simultaneous elimination of SO2 and H2S from exhaust gases, in which the exhaust gases, in a first stage (1), are brought into contact in countercurrent with a first suspension (5a), which contains 60 to 95 g/l of ZnSO3 and 80 to 90 g/l of ZnO and 0.1 to 10 g/l of ZnS. 40 to 60% by volume of the suspension (8) produced in the sump (1b) of the first stage (1) are circulated and are recycled to the head (1a) of the first stage (1). The SO2- and H2S-depleted exhaust gas (9), in a second stage (2), is brought into contact in countercurrent with a second suspension (6), which contains 80 to 150 g/l of ZnO, and with a third suspension (5), which contains 60 to 95 g/l of ZnSO3 and 80 to 90 g/l of ZnO and 0.1 to 1.0 g/l of ZnS, 40 to 60% by volume of the suspension (5) produced in the sump (2b) of the second stage (2) being circulated and recycled to the head (2a) of the second stage (2) as the third suspension (5b). The purified gas (10) is discharged from the second stage (2) at the head (2a). <IMAGE>

Description

Die Erfindung betrifft ein Verfahren zur simultanen Entfernung von S02 und H2S aus Abgasen.The invention relates to a method for the simultaneous removal of S0 2 and H 2 S from exhaust gases.

Werden Braunkohle, Erdgas oder Petrolkoks als Brennstoffe oder Rohstoffe für chemische Prozesse eingesetzt, so entstehen häufig Abgase, die Schwefel in gebundener Form enthalten. So fallen beispielsweise in Kraftwerken bei der Dampferzeugung, in Röstöfen bei der Schwefelsäurefabrikation sowie in Drehrohröfen bei der Herstellung von Titandioxid, Zinksulfid oder Bariumsulfid Abgase mit einer relativ hohen Konzentration an S02 oder auch H2S an, die einen Restgehalt an Sauerstoff enthalten. Zur simultanen Entfernung von S02 und H2S aus den Abgasen werden diese Schadstoffe an Adsorptionskatalysatoren katalytisch zu Schwefel umgesetzt. Dieser Schwefel wird an der Katalysatoroberfläche adsorbiert und anschließend bei einer Heißgasdesorption als Elementarschwefel hoher Reinheit gewonnen. Als Adsorptionskatalysator wird beispielsweise Aluminiumoxid verwendet (Ullmanns Enzyklopädie der technischen Chemie, 4. Auf!., Bd. 2, Seite 614).If lignite, natural gas or petroleum coke are used as fuels or raw materials for chemical processes, exhaust gases are often produced which contain sulfur in bound form. For example, in power plants in steam generation, in roasting ovens in sulfuric acid production and in rotary kilns in the production of titanium dioxide, zinc sulfide or barium sulfide, there are gases with a relatively high concentration of S0 2 or H 2 S, which contain a residual oxygen content. For the simultaneous removal of S0 2 and H 2 S from the exhaust gases, these pollutants are converted catalytically to sulfur on adsorption catalysts. This sulfur is adsorbed on the surface of the catalyst and then obtained as a high-purity elemental sulfur during hot gas desorption. Aluminum oxide, for example, is used as the adsorption catalyst (Ullmanns Encyclopedia of Industrial Chemistry, 4th edition!, Vol. 2, page 614).

Bei diesem bekannten Verfahren zur simultanen Entfernung von S02 und H2S aus Abgasen ist nachteilig, daß die Stöchiometrie der Reaktionsgleichung

Figure imgb0001
im Abgas weitgehend eingehalten werden muß. Geschieht dies nicht, können die Grenzwerte der TA Luft vom 27.2.1986 für die Schadstoffe S02 und H2S im Reingas nur mit einem relativ hohen technischen Aufwand unterschritten werden.In this known method for the simultaneous removal of S0 2 and H 2 S from exhaust gases, it is disadvantageous that the stoichiometry of the reaction equation
Figure imgb0001
 in the exhaust gas must be largely complied with. If this does not happen, the limit values of TA Luft from 27.2.1986 for the pollutants S0 2 and H 2 S in the clean gas can only be undercut with a relatively high technical effort.

Der Erfindung liegt daher die Aufgabe zugrunde, ein Verfahren zur simultanen Entfernung von S02 und H2S aus Abgasen zu schaffen, das kostengünstig durchführbar ist und mit welchem die Grenzwerte der TA Luft vom 27.2.1986 für S02 und H2S im Reingas relativ weit unterschritten werden.The invention is therefore based on the object to provide a method for the simultaneous removal of S0 2 and H 2 S from exhaust gases which can be carried out inexpensively and with which the limit values of TA Luft from 27.2.1986 for S0 2 and H 2 S in clean gas fall relatively short.

Die der Erfindung zugrundeliegende Aufgabe wird dadurch gelöst, daß das S02 und H2S enthaltende Abgas in einer ersten Stufe mit einer ersten Suspension, die 60 bis 95 g/I ZnS03 und 80 bis 90 g/I ZnO und 0,1 bis 1,0 g/I ZnS enthält, im Gegenstrom in Kontakt gebracht wird, wobei 40 bis 60 Vol-% der im Sumpf der ersten Stufe anfallenden Suspension, die 20 bis 35 g/I ZnS und 130 bis 145 g/I ZnS04 und 0,1 bis 8 g/I ZnS03 enthält, aus dem Sumpf der ersten Stufe abgezogen und erneut kontinuierlich am Kopf der ersten Stufe in die erste Stufe eingespeist werden, daß das in der ersten Stufe von S02 und H2S abgereicherte Abgas am Kopf der ersten Stufe abgezogen und in einer zweiten Stufe mit einer zweiten Suspension, die 80 bis 150 g/I ZnO enthält, und mit einer dritten Suspension, die 60 bis 95 g/I ZnS03 und 80 bis 90 g/I ZnO und 0,1 bis 1,0 g/I ZnS enthält, im Gegenstrom in Kontakt gebracht wird, wobei als dritte Suspension 40 bis 60 Vol-% der im Sumpf der zweiten Stufe anfallenden Suspension, die 60 bis 95 g/I ZnS03 und 80 bis 90 g/I ZnO und 0,1 bis 1,0 g/I ZnS enthält, aus dem Sumpf der zweiten Stufe abgezogen und erneut kontinuierlich am Kopf der zweiten Stufe in die zweite Stufe eingespeist werden, daß als erste Suspension 60 bis 40 Vol-% der im Sumpf der zweiten Stufe anfallenden Suspension am Kopf der ersten Stufe eingespeist werden und daß das Reingas am Kopf der zweiten Stufe abgeführt wird.The object on which the invention is based is achieved in that the exhaust gas containing S0 2 and H 2 S in a first stage with a first suspension containing 60 to 95 g / l ZnS0 3 and 80 to 90 g / l ZnO and 0.1 to 1.0 g / l of ZnS is brought into contact in countercurrent, 40 to 60% by volume of the suspension obtained in the bottom of the first stage containing 20 to 35 g / l of ZnS and 130 to 145 g / l of ZnS0 4 and Contains 0.1 to 8 g / l of ZnS0 3 , withdrawn from the bottom of the first stage and again continuously fed into the first stage at the top of the first stage, so that the exhaust gas depleted in the first stage of S0 2 and H 2 S Head of the first stage is withdrawn and in a second stage with a second suspension containing 80 to 150 g / l ZnO and with a third suspension containing 60 to 95 g / l ZnSO 3 and 80 to 90 g / l ZnO and 0 Contains 1 to 1.0 g / l of ZnS, is brought into contact in countercurrent, the third suspension being 40 to 60% by volume in the bottom of the second stage The suspension containing 60 to 95 g / l of ZnS0 3 and 80 to 90 g / l of ZnO and 0.1 to 1.0 g / l of ZnS is withdrawn from the bottom of the second stage and again continuously at the top of the second stage the second stage are fed in, that 60 to 40% by volume of the suspension obtained in the bottom of the second stage are fed in at the top of the first stage as the first suspension and that the clean gas is removed at the top of the second stage.

Als erste und zweite Stufe werden Füllkörperkolonnen verwendet. Bei den in der ersten und zweiten Stufe im Kreislauf geführten Suspensionen handelt es sich um wäßrige Suspensionen, deren pH-Werte bei 2,0 bis 5,5 liegen. Es hat sich in überraschender Weise gezeigt, daß mit dem erfindungsgemäßen Verfahren die Schadstoffe H2S und S02 fast vollständig aus Abgasen entfernt werden, auch wenn sie in schwankendem Konzentrationsverhältnis zueinander im Abgas vorhanden sind. Das erfindungsgemäße Verfahren ermöglicht infolge der relativ hohen mittleren Berieselungsdichte von 20 bis 60 m3/(m2.h) in der ersten und zweiten Stufe eine weitgehend quantitative Umsetzung der Reaktionspartner, so daß die Entfernung der Schadstoffe H2S und S02 aus Abgasen kostengünstig durchgeführt wird.Packed columns are used as the first and second stage. The suspensions circulated in the first and second stages are aqueous suspensions whose pH values are 2.0 to 5.5. It has surprisingly been found that with the method according to the invention, the pollutants H 2 S and S0 2 are almost completely removed from exhaust gases, even if they are present in the exhaust gas in a fluctuating concentration ratio. The method according to the invention enables a largely quantitative reaction of the reactants in the first and second stages due to the relatively high mean sprinkling density of 20 to 60 m 3 / (m 2 .h), so that the removal of the pollutants H 2 S and S0 2 from exhaust gases is carried out inexpensively.

Eine bevorzugte Ausgestaltung der Erfindung besteht darin, daß als erste Stufe und/oder als zweite Stufe geordnete Waschsäulen verwendet werden. Unter dem Begriff "geordnete Waschsäulen" sind diejenigen Füllkörperkolonnen zu verstehen, in welchen die Füllkörper ihrer geometrischen Form entsprechend nach einem bestimmten System angeordnet sind. Dabei können auch Füllkörper-Packungen, die aus vorgefertigten, geordneten Elementen bestehen, verwendet werden. Werden als erste Stufe und/oder zweite Stufe geordnete Waschsäulen verwendet, so wird der Druckverlust in den einzelnen Stufen in vorteilhafter Weise verkleinert.A preferred embodiment of the invention consists in using ordered washing columns as the first stage and / or as the second stage. The term “ordered washing columns” is to be understood as meaning those packed columns in which the packed bodies are arranged according to a certain system in accordance with their geometric shape. Packings consisting of prefabricated, ordered elements can also be used. If ordered wash columns are used as the first stage and / or the second stage, the pressure loss in the individual stages is advantageously reduced.

Gemäß einer weiteren bevorzugten Ausgestaltung der Erfindung ist die zweite Stufe auf der ersten Stufe innerhalb einer Trennkolonne angeordnet. Dies hat den Vorteil, daß bei der Anordnung der ersten und zweiten Stufe Rohrleitungen eingespart werden, was zu einer weiteren Reduzierung der Verfahrenskosten führt.According to a further preferred embodiment of the invention, the second stage is arranged on the first stage within a separation column. This has the advantage that pipelines are saved in the arrangement of the first and second stages, which leads to a further reduction in process costs.

Nach einer weiteren bevorzugten Ausgestaltung der Erfindung wird ein Teil der im Sumpf der ersten Stufe anfallenden Suspension aus der ersten Stufe abgeführt und mit 48 bis 97%iger H2S04 bis zu einem pH-Wert von 0,6 bis 1,0 versetzt. Dabei entsteht ein Gemisch aus S02 und H2S gemäß den folgenden Reaktionsgleichungen:

Figure imgb0002
Figure imgb0003
Das Gemisch aus S02 und H2S kann in einer Schwefelsäurefabrik weiterverarbeitet werden, wobei H2S zunächst mit Luft zu S02 oxidiert wird.According to a further preferred embodiment of the invention, part of the suspension obtained in the bottom of the first stage is removed from the first stage and 48 to 97% H 2 S0 4 is added to a pH of 0.6 to 1.0. This creates a mixture of S0 2 and H 2 S according to the following reaction equations:
Figure imgb0002
Figure imgb0003
 The mixture of S0 2 and H 2 S can be processed further in a sulfuric acid factory, H 2 S being first oxidized to S0 2 with air.

Gemäß einer weiteren bevorzugten Ausgestaltung der Erfindung wird ein Teil der im Sumpf der ersten Stufe anfallenden Suspension aus der ersten Stufe abgeführt und mit Cl2 bis zu einem pH-Wert von 1,3 bis 1,8 versetzt. Dabei laufen die folgenden chemischen Reaktionen ab:

Figure imgb0004
Figure imgb0005
 According to a further preferred embodiment of the invention, part of the suspension obtained in the bottom of the first stage is removed from the first stage and Cl 2 is added to a pH of 1.3 to 1.8. The following chemical reactions take place:
Figure imgb0004
Figure imgb0005

Der bei der Chlorierung anfallende Schwefel wird anschließend aus der Lösung abfiltriert.The sulfur resulting from the chlorination is then filtered off from the solution.

Der Gegenstand der Erfindung wird nachfolgend anhand der Zeichnung (Figur) näher erläutert.The object of the invention is explained in more detail with reference to the drawing (figure).

Die Figur zeigt den schematischen Aufbau einer Kolonne mit der ersten und zweiten Stufe.The figure shows the schematic structure of a column with the first and second stage.

In der Figur ist eine Kolonne (11) dargestellt, in welcher die erste Stufe (1) und die zweite Stufe (2) übereinander angeordnet sind. Das S02 und H2S enthaltende Abgas (4) wird horizontal in die erste Stufe (1) geleitet und mit einer Suspension (5a), die ZnS03, ZnO und ZnS enthält, im Gegenstrom in Kontakt gebracht. Dabei laufen die folgenden chemischen Reaktionen ab, wobei der benötigte Sauerstoff dem Abgas entnommen wird:

Figure imgb0006
Figure imgb0007
Figure imgb0008
Im Sumpf (1 b) der ersten Stufe (1) fällt dabei eine Suspension (8) an, die ZnS, ZnS04 und ZnS03 enthält. Diese Suspension (8) wird aus dem Sumpf (1b) der ersten Stufe (1) aus der Kolonne (11) abgeführt. Ein Teil (8b) dieser Suspension (8) wird über eine Pumpe (13) dem Kopf (1a) der ersten Stufe (1) zugeführt und erneut mit dem S02 und H2S enthaltenden Abgas (4) im Gegenstrom in Kontakt gebracht. Der andere Teil (8a) der Suspension (8) wird über den Dreiwegehahn (12) aus dem System abgeführt und entweder durch Zusatz von H2S04 oder Cl2 aufgearbeitet. Das von S02 und H2S abgereicherte Abgas (9) wird am Kopf (1a) der ersten Stufe (1) abgeführt und über dem Sumpf (2b) der zweiten Stufe (2) zugeführt. In der zweiten Stufe (2) wird das von S02 und H2S abgereicherte Abgas (9) mit einer zweiten Suspension (6), die ZnO enthält und mit einer dritten Suspension (5b), die ZnO, ZnS03 und ZnS enthält, im Gegenstrom in Kontakt gebracht. Als dritte Suspension (5 b) wird dabei ein Teil der im Sumpf (2 b) der zweiten Stufe (2) anfallenden Suspension (5) verwendet. Vor der Einspeisung der zweiten Suspension (6) und der dritten Suspension (5b) in die zweite Stufe (2) werden die Suspensionen (6) und (5b) über eine Mischstelle (7) miteinander vermischt. In der zweiten Stufe (2) reagieren die Schadstoffe H2S und S02 mit dem ZnO nach den folgenden Reaktionsgleichungen:
Figure imgb0009
Figure imgb0010
 The figure shows a column (11) in which the first stage (1) and the second stage (2) are arranged one above the other. The exhaust gas (4) containing S0 2 and H 2 S is passed horizontally into the first stage (1) and brought into contact with a suspension (5a) containing ZnS0 3 , ZnO and ZnS in countercurrent. The following chemical reactions take place, with the required oxygen being removed from the exhaust gas:
Figure imgb0006
Figure imgb0007
Figure imgb0008
 In the swamp (1 b) of the first stage (1), a suspension (8) is obtained which contains ZnS, ZnS0 4 and ZnS0 3 . This suspension (8) is removed from the bottom (1b) of the first stage (1) from the column (11). A portion (8b) of this suspension (8) is fed to the head (1a) of the first stage (1) via a pump (13) and again brought into contact with the exhaust gas (4) containing SO 2 and H 2 S in countercurrent. The other part (8a) of the suspension (8) is removed from the system via the three-way valve (12) and worked up either by adding H 2 S0 4 or Cl 2 . The depleted of S0 2 and H 2 S exhaust gas (9) is removed at the top (1a) of the first stage (1) and fed to the second stage (2) above the sump (2b). In the second stage (2) the exhaust gas (9) depleted of SO 2 and H 2 S is mixed with a second suspension (6) containing ZnO and with a third suspension (5b) containing ZnO, ZnS0 3 and ZnS, brought into contact in countercurrent. Part of the suspension (5) obtained in the sump (2 b) of the second stage (2) is used as the third suspension (5 b). Before the second suspension (6) and the third suspension (5b) are fed into the second stage (2), the suspensions (6) and (5b) are mixed with one another via a mixing point (7). In the second stage (2) the pollutants H 2 S and S0 2 react with the ZnO according to the following reaction equations:
Figure imgb0009
Figure imgb0010

Der andere Teil (5a) der Suspension (5) wird über den Dreiwegehahn (3) abgeführt und am Kopf (1a) in die erste Stufe (1) eingespeist. Das Reingas (10) wird am Kopf (2a) aus der zweiten Stufe abgeführt.The other part (5a) of the suspension (5) is discharged via the three-way valve (3) and fed into the first stage (1) at the head (1a). The clean gas (10) is discharged from the second stage at the head (2a).

Die Erfindung wird nachfolgend anhand eines Beispiels näher beschrieben.The invention is described in more detail below using an example.

Beispielexample

700 m3/h eines Abgases (4), das 980 mg/Nm3 tr. S02 und 300 mg/Nm3 tr. H2S enthält, werden einer ersten Stufe (1), die als eine geordnete Waschsäule ausgebildet ist, zugeführt und im Gegenstrom mit 5 m3/h einer ersten Suspension (5a), die 62,7 g/I ZnS03, 85,5 g/I ZnO und 0,3 g/I ZnS enthält, in Kontakt gebracht. In der ersten Stufe (1) beträgt der mittlere pH-Wert 2,0. Die Berieselungsdichte beträgt in der ersten Stufe (1) 40 m3/(m2.h). Von der im Sumpf der ersten Stufe (1) anfallenden Suspension (8), die 34,3 g/I ZnS und 0,9 g/I ZnS03 und 135,9 g/1 ZnS04 enthält, werden 60 Vol-% abgeführt und erneut am Kopf (1a) der ersten Stufe (1) mit dem Abgas im Gegenstrom in Kontakt gebracht. 40 Vol-% der im Sumpf (1b) der ersten Stufe (1) anfallenden Suspension (8) werden aus dem System abgeführt und durch Zugabe von H2S04 aufgearbeitet. Das an S02 und H2S abgereicherte Abgas (9), das einen S02-Gehalt von 850 mg/Nm3 tr. und einen H2S-Gehalt von 200 mg/Nm3 tr. aufweist, wird dem Sumpf (2 b) der zweiten Stufe (2) zugeführt. Diese zweite Stufe (2) ist ebenfalls als geordnete Waschsäule ausgebildet. Das an S02 und H2S abgereicherte Abgas (9) wird in der zweiten Stufe mit 5 m3/h einer Suspension (6), die 117 g/I ZnO enthält und mit 4,8 m3/h einer dritten Suspension (5 b), die 62,7 g/I ZnS03, 85,5 g/I ZnO und 0,3 g/I ZnS enthält und die der im Sumpf (2 b) der zweiten Stufe (2) anfallenden Suspension (5) entnommen wird, im Gegenstrom in Kontakt gebracht. Der mittlere pH-Wert der zweiten Stufe liegt zwischen 5,0 und 5,5. Die Berieselungsdichte in der zweiten Stufe (2) beträgt 40 m3/(m2.h). Die verbleibenden 5 m3/h der im Sumpf (2 b) der zweiten Stufe (2) anfallenden Suspension (5) werden aus der zweiten Stufe (2) abgeführt und als erste Suspension (5 a) in die erste Stufe (1) am Kopf (1 a) eingespeist. Das am Kopf (2a) der zweiten Stufe (2) abgeführte Reingas (10) hat einen S02 -Gehalt von 70 mg/Nm3 tr. und einen H2S-Gehalt von 1 mg/Nm3 tr. (tr = trocken).700 m 3 / h of an exhaust gas (4), which contains 980 mg / Nm 3 dry SO 2 and 300 mg / Nm 3 dry H 2 S, are a first stage (1), which is designed as an ordered wash column, supplied and brought into contact in countercurrent with 5 m 3 / h of a first suspension (5a) containing 62.7 g / l ZnS0 3 , 85.5 g / l ZnO and 0.3 g / l ZnS. In the first stage (1) the average pH is 2.0. The sprinkling density in the first stage (1) is 40 m 3 / (m 2 .h). 60% by volume are removed from the suspension (8) obtained in the bottom of the first stage (1), which contains 34.3 g / l ZnS and 0.9 g / l ZnS0 3 and 135.9 g / l ZnS0 4 and again brought into contact with the exhaust gas in countercurrent at the head (1a) of the first stage (1). 40% by volume of the suspension (8) obtained in the sump (1b) of the first stage (1) are removed from the system and worked up by adding H 2 SO 4 . The exhaust gas (9) depleted in S0 2 and H 2 S, which has an S0 2 content of 850 mg / Nm 3 dr. And an H 2 S content of 200 mg / Nm 3 dr., Is added to the sump (2 b) fed to the second stage (2). This second stage (2) is also designed as an ordered wash column. The exhaust gas (9) depleted in SO 2 and H 2 S is in the second stage with 5 m 3 / h of a suspension (6) which contains 117 g / l of ZnO and with 4.8 m 3 / h of a third suspension ( 5 b), which contains 62.7 g / I ZnS0 3 , 85.5 g / I ZnO and 0.3 g / I ZnS and that of the suspension (5) obtained in the sump (2 b) of the second stage (2) is removed, brought into contact in countercurrent. The average pH of the second stage is between 5.0 and 5.5. The sprinkling density in the second stage (2) is 40 m 3 / (m 2 .h). The remaining 5 m 3 / h of the suspension (5) obtained in the sump (2 b) of the second stage (2) are removed from the second stage (2) and as the first suspension (5 a) in the first stage (1) Head (1 a) fed. That on the head (2a) of the second stage (2) removed clean gas (10) has an S0 2 content of 70 mg / Nm 3 dr. and an H 2 S content of 1 mg / Nm 3 dr. (tr = dry).

Mit dem erfindungsgemäßen Verfahren werden somit die Grenzwerte der TA Luft vom 27.2.1986 für H2S (5 mg/Nm3) und S02 (500 mg/Nm3) relativ weit unterschritten.With the method according to the invention, the limit values of TA Luft from 27.2.1986 for H 2 S (5 mg / Nm 3 ) and S0 2 (500 mg / Nm 3 ) are thus relatively far below.

Claims (5)

1. Verfahren zur simultanen Entfernung von S02 und H2S aus Abgasen, dadurch gekennzeichnet, daß das S02 und H2S enthaltende Abgas (4) in einer ersten Stufe (1) mit einer ersten Suspension (5a), die 60 bis 95 g/I ZnS03 und 80 bis 90 g/1 ZnO und 0,1 bis 1,0 g/I ZnS enthält, im Gegenstrom in Kontakt gebracht wird, wobei 40 bis 60 Vol-% der im Sumpf (1 b) der ersten Stufe (1) anfallenden Suspension (8), die 20 bis 35 g/I ZnS und 130 bis 145 g/I ZnS04 und 0,1 bis 8 g/I ZnS03 enthält, aus dem Sumpf (1b) der ersten Stufe (1) abgezogen und erneut kontinuierlich am Kopf (1a) der ersten Stufe (1) in die erste Stufe (1) eingespeist werden, daß das in der ersten Stufe (1) von S02 und H2S abgereicherte Abgas (9) am Kopf (1a) der ersten Stufe (1) abgezogen und in einer zweiten Stufe (2) mit einer zweiten Suspension (6), die 80 bis 150 g/I ZnO enthält, und mit einer dritten Suspension (5b), die 60 bis 95 g/I ZnS03 und 80 bis 90 g/1 ZnO und 0,1 bis 1,0 g/I ZnS enthält, im Gegenstrom in Kontakt gebracht wird, wobei als dritte Suspension (5 b) 40 bis 60 Vol-% der im Sumpf (2 b) der zweiten Stufe (2) anfallenden Suspension (5), die 60 bis 95 g/I ZnS03 und 80 bis 90 g/I ZnO und 0,1 bis 1,0 g/I ZnS enthält, aus dem Sumpf (2b) der zweiten Stufe (2) abgezogen und erneut kontinuierlich am Kopf (2a) der zweiten Stufe (2) in die zweite Stufe (2) eingespeist werden, daß als erste Suspension (5 a) 60 bis 40 Vol-% der im Sumpf (2 b) der zweiten Stufe (2) anfallenden Suspension (5) am Kopf (1a) der ersten Stufe (1) eingespeist werden und daß das Reingas (10) am Kopf (2a) der zweiten Stufe (2) abgeführt wird.1. A process for the simultaneous removal of S0 2 and H 2 S from exhaust gases, characterized in that the exhaust gas (4) containing S0 2 and H 2 S in a first stage (1) with a first suspension (5a) which is 60 to Contains 95 g / I ZnS0 3 and 80 to 90 g / 1 ZnO and 0.1 to 1.0 g / I ZnS, is brought into contact in countercurrent, with 40 to 60% by volume of the sump (1 b) first stage (1) resulting suspension (8), which contains 20 to 35 g / l ZnS and 130 to 145 g / l ZnS0 4 and 0.1 to 8 g / l ZnS0 3 , from the sump (1b) of the first stage (1) deducted and again continuously fed at the top (1a) of the first stage (1) into the first stage (1) that the exhaust gas (9) depleted in the first stage (1) of S0 2 and H 2 S The head (1a) of the first stage (1) is drawn off and in a second stage (2) with a second suspension (6) which contains 80 to 150 g / l of ZnO and with a third suspension (5b) which is 60 to 95 g / I ZnS0 3 and 80 to 90 g / 1 ZnO and 0.1 to 1.0 g / I ZnS contains, in countercurrent is brought into contact, the third suspension (5 b) being 40 to 60% by volume of the suspension (5) obtained in the sump (2 b) of the second stage (2), the 60 to 95 g / l of ZnSO 3 and 80 to Contains 90 g / l ZnO and 0.1 to 1.0 g / l ZnS, withdrawn from the sump (2b) of the second stage (2) and again continuously at the top (2a) of the second stage (2) into the second stage (2) are fed in that 60 to 40% by volume of the suspension (5) obtained in the sump (2 b) of the second stage (2) at the top (1a) of the first stage (1) is fed in as the first suspension (5 a) and that the clean gas (10) at the head (2a) of the second stage (2) is removed. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß als erste Stufe (1) und/oder als zweite Stufe (2) geordnete Waschsäulen verwendet werden.2. The method according to claim 1, characterized in that as the first stage (1) and / or as the second stage (2) ordered wash columns are used. 3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß die zweite Stufe (2) auf der ersten Stufe (1) innerhalb einer Trennkolonne (11) angeordnet ist.3. The method according to claim 1 or 2, characterized in that the second stage (2) on the first stage (1) is arranged within a separation column (11). 4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß ein Teil der im Sumpf der ersten Stufe (1) anfallenden Suspension (8) aus der ersten Stufe (1) abgeführt wird und mit 48 bis 97%iger H2S04 bis zu einem pH-Wert von 0,6 bis 1,0 versetzt wird.4. The method according to any one of claims 1 to 3, characterized in that part of the suspension (8) obtained in the bottom of the first stage (1) is removed from the first stage (1) and with 48 to 97% H 2 S0 4 is added to a pH of 0.6 to 1.0. 5. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß ein Teil der im Sumpf der ersten Stufe (1) anfallenden Suspension (8) aus der ersten Stufe (1) abgeführt wird und mit Cl2 bis zu einem pH-Wert von 1,3 bis 1,8 versetzt wird.5. The method according to any one of claims 1 to 3, characterized in that part of the suspension (8) obtained in the bottom of the first stage (1) is removed from the first stage (1) and with Cl 2 to a pH value is shifted from 1.3 to 1.8.
EP91201757A 1990-07-27 1991-07-05 Simultaneous elimination of SO2 and H2S from off gases Expired - Lifetime EP0469659B1 (en)

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DE4023926A DE4023926A1 (en) 1990-07-27 1990-07-27 Simultaneous removal of sulphur di:oxide and hydrogen sulphide - from waste gas by two=stage countercurrent contact with suspension contg. zinc oxide and prods.
DE4023926 1990-07-27

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US8902860B2 (en) 2006-01-11 2014-12-02 Qualcomm Incorporated Wireless communication methods and apparatus using beacon signals
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CN102008886A (en) * 2010-11-22 2011-04-13 浙江双屿实业有限公司 Zinc oxide wet turbulent washing flue gas desulfurization device and process
CN102716657A (en) * 2012-06-13 2012-10-10 河南豫光锌业有限公司 Zinc oxide desulfurization method applicable to zinc smelting system

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ES2055519T3 (en) 1994-08-16
EP0469659B1 (en) 1994-06-08
CA2047660A1 (en) 1992-01-28
DE4023926C2 (en) 1993-06-03
ATE106769T1 (en) 1994-06-15
DE4023926A1 (en) 1992-01-30

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